The reaction of polyoxometalate anion [GeW11O39]8− with the complex anion [MoV2O4(H2O)2(ox)2]2− in the presence of CuCl2·2H2O and DMF (DMF = N,N-dimethyl formamide) at 85 °C in aqueous solution produces both a two-dimensional heteropoly blue H2[α-GeW10MoV2O40][Cu(DMF)3H2O]2·5H2O (1) and a three-dimensional heteropoly blue H4[α-GeW10MoV2O40]2 [CuK2(DMF)6] [K4(DMF)6] (2), which demonstrates that different molar ratio of W : Cu in the reaction could conduct different multidimensional structures of 2D and 3D. The magnetic investigation of the two compounds in temperature range from 300 K to 2 K indicated the presence of strong antiferromagnetic interactions related with the two MoV ions in these two compounds.